본 연구에서는 수용성 아크릴을 합성한 다음 수성 카제인 수지를 합성하여 기합성 완성된 아크릴 수지에 카제인 수지의 적하량을 점차 증가시켜 변화하는 물성을 피혁(Lamb leather)에 표면 코팅하여 물성을 측정 분석하였다. 내용제성 측정 결과 높은 내용제성 물성을 지닌 아크릴 수지와 카제인 수지의 함량이 물성 변화에 끼치지 않았으며 모두 높은 물성치를 나타내었다. 인장 강도 측정치에서는 아크릴 단독 코팅의 측정치가 1.399kgf/mm2로 가장 낮은 수치를 나타내었으며, 카제인 수지의 합량이 제일 높은 WAC-3가 가장 높은 인장력 1.426kgf/mm2을 나타내었다. 또한 내마모도 측정에서는 WAC-3가 제일 높은 69.774 mg.loss로 우수한 물성변화를 나타내었고, 연실률의 경우 아크릴 단독 코팅인 WAR이 820 %로 가장 높은 수치를 나타내었다.

In order to synthesize high-solid coatings, acrylic resins (HSAs) containing 90% solid content were first synthesized, then the synthesized HSAs were cured with a curing agent, isocyanate, at room temperature to obtain high-solid coatings. In the HSAs synthesis, conversion was in a range of 82~87%, and viscosities and number-averaged molecular weight (Mn) of the HSAs were in a range of 4380~8010 cP and 1540~1660, respectively. From the correlation between Tg value, viscosity and Mn, it was found that, with increasing Tg value, viscosity increases rapidly and molecular weight increases slowly. From the visco-elasity measured by the pendulum method, it was found that the curing time decreased with increasing Tg values. From the tests of physical properties of the coatings' film, 60˚ specular gloss, impact resistance and heat resistance were proved to be good and pencil hardness, drying time and pot-life were proved to be poor.

To prepare weather-resistant modified silane acrylic resin coatings for an architectural purpose, tetrapolymers were synthesized by radical polymerization. 3-Methacryloxypropyltrimethoxysilane (MPTS) as a silicone monomer and n-butyl acrylate, methyl methacrylate, and n-butyl methacrylate as acrylic monomers were used. The composition of monomers was adjusted to fix the glass transition temperature of acrylic polymer for 20℃. The composition of MPTS in the synthesized polymer were varied from 10 wt% to 30 wt%. On the basis of synthesized resin amber paints were prepared and their physical properties and effects on weatherability were examined. The presence of MPTS in modified silane acrylic resins generally resulted in low molecular weight and broad molecular weight distribution, and also lowered the viscosity of the copolymers. The coated films prepared from these resins showed good and balanced properties in general. Adhesion to the substrate was outstanding in particular. Weatherability tests were carried out in three different types such as outdoor exposure, QUV, and SWO. The test results showed that the modified silane acrylic resins containing 30 wt% of MPTS had superior weathering properties.

Three different weather-resistant coatings were fabricated with the various weight ratios of a mill-base silicone/acrylic resin to let-down silicone /acrylic resin at 2:8, 3:7, and 4:6 respectively. The prepared coatings were tested to investigate the effect of composition of weather-resistant coatings on the physical properties. The thermal stability, salt spray exposure, and weather-resistance were improved with the increased silicone content. It was concluded that the optimum retio of mill-base silicone/acrylic resin to let-down silicone/acrylic resin would be 2:8 and the coating with 30 wt% of silicone content would have high weather-resistance.

In order to prepare high-solid coatings, acrylic resins, HSCs [poly (EA/EMA/2-HEMA/CLA)] that contain 90% solid, were synthesized by copolymerization of ethyl acrylate (EA), ethyl methacrylate (EMA), 2-hydroxyethyl methacrylate (2-HEMA) and caprolactone acrylate (CLA). The high-solid coatings named as CHSCs (HSCs/HDI-trimer) were prepared by the curing reaction between the acrylic resins containing 90% solid contents and the isocyanates (HDI-trimer) curing agent room temperature. The curing behavior and various properties were examined on the film coated with the both high-solid coatings. The glass transition temperatures (Tg) of CHSCs increased proportionally with increasing the predicted Tg value by Fox equation, and had nothing to do with the solid contents. The prepared film showed good properties for 60˚ specular gloss, impact resistance, cross-hatch adhesion and heat resistance, and bad properties for pencil hardness, drying time, and pot-life. Among the film properties, the heat resistance was very excellent and could be explained by the introduction of functional monomers of CLA.

To prepare weather-resistant silicone/acrylic resin coatings for an architectural purpose, tetrapolymers were synthesized by a radical polymerization. 3-Methacryloxypropyltrimethoxysilane (MPTS) as a silicone monomer and n-butyl acrylate, methyl methacrylate, and n-butyl methacrylate as acrylic monomers were used. The compositions of monomers were adjusted to fix the glass transition temperature of acrylic polymer for 20℃. The composition of MPTS in the synthesized polymer were varied from 10 wt% to 30 wt%. On the basis of synthesized resin amber paints were prepared and their physical properties and effects for weatherability were examined. The presence of MPTS in silicone/acrylic resins generally resulted in low molecular weight and broad molecular weight distribution, and also lowered the viscosity of the copolymers. The coated films prepared from these resins showed good and balanced properties in general. Adhesion to the substrate was outstanding in particular. Weatherability tests were carried out in three different types such as outdoor exposure, QUV, and SWO. The test results showed that the silicone/acrylic resins containing 30 wt% of MPTS had weather-resistant properties.

In order to prepare high-solid coatings, first acrylic resins (HSAs) which contain 80% solid were synthesized, and then the prepared resins were cured with isocyanate at room temperature. In the synthesis of HSAs, viscosity, number average molecular weight (Mn) and conversion were 1372~2700 cps, 1520~1650 and 83~87%, respectively. Among the four kinds of initiators used, tert-amylperoxy-2-ethyl hexanoate was the most proper one in the synthesis of HSAs. With increasing Tg values, viscosity increased rapidly and molecular weight increased slowly. As a result of the examination of coated films, it was found that 60˚ specular gloss, impact resistance, heat resistance and cross-hatch adhesion were good, and pencil hardness, drying time and pot life were poor.

The high-solid coatings were prepared by blending the synthesized acrylic resin in the previous paper, and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. The 60˚ specular gloss, impact resistance, cross-hatch adhesion, and heat resistance of the films proved to be good, and the pencil hardness, drying time, and pot-life proved to be slightly poor. From a viscoelastic measurement using a rigid-body pendulum, curing was accelerated with the Tg value.

Acrylic resins (HSCs : EA/EMA/2-HEMA/CLA) which contain 80% solid content were synthesized by the copolymerization of monomers (ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate) and functional monomer (caprolactone acrylate : CLA) which improves the crosslinking density and physical properties of films. The physical properties of the prepared acrylic resins (HSCs) containing CLA, are as follows: viscosity 1440~2630 cps ; Mn 1590~1660 ; and conversions, 81~86%, respectively. From the correlation of Tg values, viscosities, and Mn of the HSCs, it was found thst viscosity and Mn increased with Tg value.

Copolymers (HSA-98-20, HSA-98-0, HSA-98+20) which are acrylic resin containing 80% solid content were synthesized by the reaction of monomers, including methyl methacrylate, n-butyl acrylate, and 2-hydroxyethyl acrylate with a functional monomer, such as acetoacetoxyethyl methacrylate (AAEM), which may improve in cross-linking density and physical properties of films. The physical properties of prepared acrylic resins, containing AAEM, are as follows : viscosity, 1420~5760cps ; number average molecular weight, 2080~2300 ; polydispersity index, 2.07~2.19 ; conversions, 88~93%, respectively. To prepare acryl resins, four kinds of initiators including α,α'-azobisisobutyronitirile (AIBN), di-tert-butyl peroxide (DTBP), t-amylperoxy-2-ethyl hexanoate (APEH), benzoyl peroxide (BPO) were used. The viscosity of the acrylic resins prepared with these initiators was increased in the order of DTBP〉APEH〉AIBN〉BPO. APEH was proved as a suitable initiator in this study. Shear rates of acrylic resins were constant in respect to viscosity. From these results, it would appear that the resins have Newtonian flow characteristics and good workability.

High-solid coatings were prepared by blending of previosly synthesized acrylic resins and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. The impact resistance, cross-hatch adhesion, 60˚specular gloss, and heat resistance of the films proved to be good, and the pencil hardness and drying time proved to be slightly poor. Especially, there was a remarkable improvement in the heat resistance. This improvement may stem from the regular arrangement of ethyl groups introduced into the acrylic resin. As a result of Rigid-body pendulum visco-elasticity measurement, dynamic Tg values of cured films increased with dynamic Tg values.

Acrylic resins (HSCs : EA/EMA/2-HEMA/CLA) which contain 70% solid content were synthesized by the copolymerization of monomers (2-hydroxyethyl methacrylate, ethyl acrylate, and ethyl methacrylate) and functional monomer (caprolactone acrylate : CLA) which improves the crosslinking density and physical properties of films. The physical properties of the prepared acrylic resins (HSCs) containing CLA, are as follows : viscosity 245~515 cps ; Mn 2670~2840 ; and conversions, 83~91%, respectively. From the correlation of Tg values, viscosities, and Mn of the HSCs, it was found that viscosity and Mn increased with Tg value.

The high-solid coatings were prepared by blending the synthesized acrylic resin in the previous paper and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. The impact resistance, 60℃ specular gloss, cross-hatch adhension, and heat resistance of the films proved to be good, and the pencil hardness and drying time proved to be slightly poor. Especially, there was a remarkable improvement in the heat resistance. This improvement may stem from the regular arrangement of ethyl groups introduced into the acrylic resin. From a viscoelastic measurement using a rigid-body pendulum, curing was accelerated with the Tg value. With the increase in Tg, log damp value was lowered and dynamic viscoelasic Tg of a cured film was increased.

A copolymer 〈HSAs : EA/EMA/2-HEMA/AAEM) which is an acrylic resin containing 70% solid content was synthesized by the reaction of monomers, including ethyl acrylate, ethyl methacrylate, and 2-hydroxyethyl methacrylate with a functional monomer, such as acetoacetoxyethyl methacrylate, which may give improvements in cross-linking density and physical properties of films. The physical properties of prepared acrylic resins, HSA containing AAEM, are as follows : viscosity, 203~550cps ; Mn, 2590~2850 ; and conversion, 82~89%, respectively. It was found from the plotting of Tg versus viscosity and Tg versus molecular weight that viscosity increased with Tg while number averaged molecular weight decreased with increasing Tg.

An acrylic resin was synthesized with several monomers, styrene(St), 2-hydroxyethyl methacrylate(2-HEMA), n-butyl acrylate, methyl methacrylate, and acetoacetoxyethl methacrylate(AAEM) to prepare a high-solid coatings. Then, a high-solid acryl/melamine coatings was prepared by curing the acrylic resin with a curing agent, hexamethoxymethylmelamine(HMMM). The curing behavior of the acrylic resin with HMMM was investigated by the Ozawa method using DSC. For AAEM/HMMM and 2-HEMA/HMMM curing reactions, activation energies were 33.01 and 27.12 kcal/mol and frequency factors were 9.54×1015 and 1.53×1013 min-1, respectively. From the results, it was found out that 2-HEMA showed higher reactivity with the curing agent than AAEM.

To prepare an environmental friendly high-solid coatings an acrylic resin containing 80% of solid content was synthesized by addition polymerization of caprolactone acrylate, n-butyl acrylate, ethyl methacrylate, and 2-hydroxyethyl methacrylate. The conversion was 78~93% and the prepared resin's physical properties are as follows: viscosity, 212~3424cps: Mn 1740~2400. There was a trend that viscosity and molecular weight of the resin increased with Tg, but no direct proportionality was observed.

The objectives of this study is to investigate the optimum reaction conditions and to identify the product formula in the synthesis of a silicone/acrylic resin that curing in moisture at room temperature. By the addition polymerization of monomers, n-butyl acrylate, methyl methacrylate, n-butyl methacrylate, and 3-methacryloxypropyltrimethoxysilane. a quarter polymer was obtained. Among various initiators investigated in this study, 2.2'-azobisisobutyronitrille was found to be the most suitable initiator. The optimum reaction conditions found in this study are 70 wt% of initial solvent amount, 120 minutes of dropping time, 3 times of initiator addition, 82~105℃ of reaction temperature, and 8 hrs of reaction time. Also, number average molecular weight of 11700~33100 and molecular weight distribution of 1.81~3.44 were obtained.